A huge variety of silver based ternary sulfide semiconductors (SCs) have been considered for the sustainable advancement of renewable energy sources. Herein, we have synthesized two important classes of newly emerging semiconductor nanocrystals (NCs) Ag₃SbS₃ (SAS), i.e. hexagonal and monoclinic by simply tuning the solvent polarity, of which the second one has been synthesized in a phase pure NC for the first time by the thermal decomposition of silver and antimony based dithiocarbamate (∼N-CS₂-M) complexes. Interestingly, these two systems exhibit two different semiconducting (SC) properties and band gaps; hexagonal SAS has a p type (E_g ∼ 1.65 eV) whereas monoclinic SAS has an n type (E_g ∼ 2.1 eV) character. For the first time ever we have designed a reducing working electrode (i.e. cathode) by modifying the rotating disc electrode (RDE) with hexagonal SAS that exhibits excellent electrochemical oxygen reduction reaction (ORR) activity (E_onset = 1.09 V vs. RHE and average number of electron transfer: 3.89) comparable to that of the highly expensive Pt/C (E_onset = 0.88 V vs. RHE and average number of electron transfer: 3.92). Density functional theory (DFT) investigation confirms the corroborations of experimental data with theoretical implications. In addition, the electrode fabricated from monoclinic SAS acts as an efficient photoanode which exhibits higher photoelectrochemical (PEC) methanol oxidation reaction (MOR) activity under illumination in alkaline medium compared to that of standard TiO₂ grown on an indium tin oxide (ITO) coated glass slide. On illumination, the relative photocurrent density at the onset potential has been obtained to be 845 which is a very significant experimental output with respect to any other TiO₂ or Pt@TiO₂ based photocatalysts for this application. The physicochemical stability and reusability of both materials were supported by 50 hours of extended electrochemical chronoamperometric measurements and powder XRD and the TEM analyses after electrocatalysis. This study explores a possible pathway for designing simple and less expensive but catalytically efficient silver based ternary sulfide NC systems for developing an SC material to reduce the energy crisis in the near future.

中文翻译：

---

一锅溶剂辅助Ag3SbS3纳米晶体的合成，并探索它们的相依电化学行为对氧还原反应和可见光诱导的甲醇氧化反应。

为了可持续发展可再生能源，已经考虑了多种多样的银基三元硫化物半导体（SC）。本文中，我们通过简单地调节溶剂极性合成了两类重要的新兴半导体纳米晶体Ag ₃ SbS ₃（SAS），即六方晶系和单斜晶系，其中第二种是在纯NC相中合成的。首次通过银和锑基二硫代氨基甲酸酯（〜N-CS ₂ -M）配合物的热分解。有趣的是，这两个系统表现出两种不同的半导体（SC）特性和带隙。六边形SAS具有p型（Ë_克〜1.65电子伏特），而单斜晶SAS具有n型（È_克〜2.1eV以上）字符。通过使用六角形SAS修改转盘电极（RDE），我们首次设计了还原性工作电极（即阴极），六角形SAS具有出色的电化学氧还原反应（ORR）活性（E_起始= 1.09 V vs. RHE和平均值电子转移数：3.89）与昂贵的Pt / C相当（E_起始= 0.88 V vs.RHE和平均电子转移数：3.92。密度泛函理论（DFT）研究证实了具有理论意义的实验数据的确证。此外，与在铟锡氧化物（ITO）涂层上生长的标准TiO ₂相比，由单斜晶SAS制成的电极可作为一种高效的光电阳极，在碱性介质下照射下表现出更高的光电化学（PEC）甲醇氧化反应（MOR）活性。幻灯片。照明时，在开始电位下的相对光电流密度已获得845，对于任何其他TiO ₂或Pt @ TiO _2来说，这是非常重要的实验输出用于该应用的光催化剂。两种材料的物理化学稳定性和可重复使用性通过50小时的扩展电化学计时安培测量，粉末XRD和电催化后的TEM分析得到支持。这项研究探索了设计简单且成本较低但具有催化效率的银基三元硫化物NC系统的可能途径，以开发SC材料以减少近期的能源危机。